Process for dyeing textiles with dyestuffs containing pyrimidine ring



United States Patent Otfice 3,097,910 Patented July 16, 1963 No Drawing.Original application June 29, 1960, Ser. No. 39,723. Divided and thisapplication Mar. 16, 1961, Ser. No. 96,099

Claims priority, application Great Britain Oct. 23, 1959 9 Claims. (Cl.854.Z)

This invention relates to new dyestufis and more particularly it relatesto new dyestuifs which are valuable for colouring natural and artificialtextile materials.

According to the invention there are provided the new dyestuffs whichcontain at least one group of the formula:

wherein A represents O--, S- or R represents a hydrogen atom or asubstituted or unsubstituted alkyl radical and X represents a pyrimidinering which is attached to A through the carbon atom in the 2- or4-position of the pyrimidine ring, and which carries a cyano, carboxy orcarboalkox group attached to the Sposition of the pyrimidine ring andwhich also carries one or two chlorine or bromine atoms attached to theremaining carbon atoms of the pyrimidine ring.

Each of the groups of Formula I, as hereinbefore defined, is attached toa carbon atom present in the dyestufit'. The said carbon atom may formpart of an aryl residue present in the dyestuif or may form part of analkyl chain which is directly attached to an aryl residue present in thedyest-ufi or is attached to an aryl residue through a bridging atom orgroup. As examples of such bridging atoms or groups there may bementioned --O-, S, -CO, SO -NH-,

Formula I The dyestulf may be a member of any known dyestuti series andpreferably it is a dyestuif of the am, which may be monoazo or polyazo,nitro, anthraquinone or phthalocyanine series, and which may or may notcontain a Water-solubilising group such as a sulphonic, oarboxylic or asulphamyl group. If desired the dyestutf may also contain coordinatelybound metal such as coordinately bound copper, chromium or cobalt.

As examples of the carboalkoxy groups which are attached to the5-position of the pyrimidine ring there may be mentioned carbo loweralkoxy groups such as carbomethoxy, canboethoxy and carbopropoxy groups.

As examples of the substituted or unsubstituted alkyl radicalsrepresented by R there may be mentioned lower alkyl radicals such asmethyl, ethyl, propyl and butyl, which may contain substituents such asmethoxy, ethoxy and hydroxy groups.

When the pyrimidine ring represented by X contains only one chlorine orbromine atom attached to one of the two remaining carbon atoms of thesaid ring then the remaining carbon atom of the said ring may beoptionally substituted by an alkyl radical which is preferably a loweralkyl radical such as ethyl and propyl and preferably a methyl radical,or by a thiocyano group or by a group of the formula:

Formula II wherein R and R" each represent substituted or unsubstitutedhydrocarbon or heterocyclic radicals, or R and R may be joined togetherto form with the nitrogen atom N a 5- or 6-membered heterocyclic ring. Rand R" preferably represent alkyl radicals, in particular lower alkylradicals such as methyl, ethyl, propyl and butyl radicals, or acycloalkyl radical, in particular the cyclohexyl radical, or amonocyclic aryl radical such as the phenyl radical.

According to a further feature of the invention there is provided aprocess for the manufacture of the new dyestulfs, as hereinbeforedefined, which comprises treating a dyestulf compound containing atleast one group of the formula: AH, wherein A has the meaning above,with a pyrimidine which contains a cyano, carboxy or carboalkoxy groupattached to the 5-position of the pyrimidine ring and which also carriestwo or three chlorine or bromine atoms attached to the remaining carbonatoms of the pyrimidine ring.

This process of the invention may be conveniently brought about byadding a solution of the pyrimidine in a water-miscible organic liquidsuch as acetone or dioxan to a solution or suspension of the dyestuficompound in water, or in a water-miscible organic liquid such as acetoneor dioxan, or in a mixture of water and/or a watermiscible organicliquid, stirring the mixture at a suitable temperature, for example at atemperature between 10 C. and C., whilst maintaining the pH of themixture between 6 and 7 by the addition of an acid-binding agent such assodium carbonate or sodium hydroxide, and

filtering off the dyestutf which is precipitated. If necessary waterand/or sodium chloride can be added to ensure complete precipitation ofall the dyestufl.

When the pyrimidine used in this process of the invention contains onlytwo chlorine or bromine atoms attached to two of the remaining 3 carbonatoms of the pyrimidine ring then the third carbon atom may optionallybe substituted by an alkyl radical or by a thiocyano group or by a groupof Formula II, as hereinbefore defined. The pyrimidines used in theprocess of the invention can therefore be represented by the formula:

Formula lII wherein T represents a cyano, carboxy or oarboalkoxy group,Y represents a chlorine or a bromine atom, one of Y and Y represents achlorine or a bromine atom, and the other Y or Y represents a hydrogen,chlorine or bromine atom, or an alkyl radical or a thiocyano group or agroup of Formula II, as Ihereinbefore defined.

The pyrimidines of Formula III wherein one of Y and Y represents achlorine or a bromine atom and the other Y or Y represents a hydrogen,chlorine or bromine atom or an alkyl radical may themselves be obtainedby treating the corresponding dior trihydroxypyrimidines with theappropriate phosphorous oxyhalide, preferably in the presence of atertiary amine such as dirnethylaniline or diethylaniline, 'for exampleas described in volume 20 of The Journal of Organic Chemistry at page837. Alternatively the pyrimidines of Formula III wherein one of Y and Yrepresents a chlorine or a bromine atom and the other Y or Y representsa hydrogen, chlorine or bromine atom or an alkyl radical andT'represents a oyano group may be obtained by treating the correspondingS-carbonamido-(dior tri-)hydroxypyrimidine with the appropriatephosphorous oxyhalide in the presence of a tertiary amine.

i Na.S.O.N

wherein R and R have the meanings stated above.

As specific examples of the pyrimidines of Formula III which can be usedin this process of the invention there may be mentioned5-cyano-2z4:6-trichloropyrimidine, 5-cyano-2 :4 6-tribromopyrimidine,5-cyano-2 :4-dichloropyrimidine, 5 cyano-2:4-dibrornopyrimidine, 5-cyano-2-methyl-4:6-dichloropyrimidine, S-oarbomethoxy- 24-diohloropyrimidine, S-carbethoxy-Z 4-dichloropyrimidine and5-carboxy-2:4-dichloropyrimidine.

Each of the AH groups present in the dyestufi compounds used in theprocess of the invention is directly attached to a carbon atom of anaryl residue present in the dyestuff compound, or each of the AH groupsis attached to a carbon atom which forms part of an alkyl radical whichis directly attached to an aryl residue present in the dyestutf compoundor is attached through a linking atom or group. As examples of suchlinking atoms or groups there may be mentioned O, --S--,

It is however preferred that each of the AH groups present in thedyestuff compound is the group NHR wherein R has the meaning statedabove.

Dyestuff compounds of the azo series containing at least one NHR group,as hereinbefore defined, which may be used in the process of theinvention may be obtained by a variety of methods. One method is todiazotise an aromatic primary amine and couple the diazonium compound soobtained with a coupling component containing an NHR group. As examplesof aromatic primary amines which may be used in this manner to obtainthe aminoazo compounds there may be mentioned aniline, mandp-toluidines, 0-, mand p-anisidines, 0-, mand p-chloroanilines,2:5-dichloroaniline, uand S-naphthylamine, 2:5-dimethylaniline,-nitro-2-aminoanisole, 4- aminodiphenyl, aniline-2-, 3- and 4-carboxylicacids, 2- aminodiphenylether, 2-, 3- or 4-arninobenzene sulphonamide orsulphonmonomethylor ethylamides or sulphondimethylor sulphondiethylamides, dehydrothio-p-toluidine monosulphonic acid ordehydrothio-p-toluidine disulphonic acid, aniline-2-, 3- and 4-sulphonicacids, aniline-2 S-disulphonic acid, 2 4-dimethylaniline-6-sulphonicacid, 3-aminobenzotrifluoride-4-sulphonic acid, 4-chloro-5methylaniline-Z-sulphonic acid, 5-chloro-4-methylaniline-2-sulphonicacid, 3-acetylaminoaniline-6-sulphonic acid,4-acetylaminoaniline-2-sulphonic acid, 4-chloroaniline-2-sulphonic acid,3:4-dichloroaniline-6-sulph-onic acid, 4-methylaniline-2-sulphonic acid,S-methylaniline- 6-sulphonic acid, 2:4dimethoxyaniline-6-sulphon-icacid, 4-methoxyaniline-2-su lphonic acid and S-methoxyaniline-2-sulphonic acid, 2:5-dichloroaniline-4-sulphonic acid, 2-naphthylamine-4:8 and 6:8-disulphonic acids, l-naphthylamine-2-, 4-, 5-,6- or 7-monosulphonic acid, l-naphthylamine-3:6-disulphonic acid,2-naphthylarnine-3z6- and 5 7-disulphonic acids, 2-naphthylamine-3 :6S-trisulph-onic acid, mand p-nitroam'line, 4-nitroaniline-2-sulphonicacid, 3nitroaniline-6-sulphonic acid, mor p-aminoacetanilide and4-amino-2-acetylaminotoluene-5-sulphonic acid.

As examples of coupling components which can be used there may bementioned Z-aminoand Z-methylamino-Snaphthol-7-sulphonic acids, 2-aminoand Z-methylamino-S-naphthol-6-sulphonic acids, l-amino and 1-ethylamino-8naphthol-6-sulphonic acids and corresponding 3:6- and4:6-disulphonic acids, 1-(3'- or -4-aminobenzoylamino)8-naphthol-3:6-and 4:6-disu lphonic acids, aniline, oand m-anisidines, 0-, andm-toluidines, 2:5-dimethylaniline, 3-amino-4-methoxytoluene,2:5-dimethoxyaniline, N-methylaniline, N-ethyl-o-toluidine,N-methyl-m-anisidine, 3methylamino4-methoxyto1uene, 1-(3-aminophenyl)-3-methyl-, -carboxy-, and carboethoxy-S- pyrazolone,1-(4-aminophenyl)-3-methyl-, -carboxy-, and -carboethoxy-5pyrazolonesand 1-(4-amino-3-carboxyphenyl)3-methyl-5-pyrazolone.

The aminoazo compounds which are to be used in the process of theinvention are not restricted to compounds containing only one azo group.Disazo compounds which may be used may be obtained for example bytetrazotisation of an aromatic diamine containing two primary aminogroups and coupling the tetrazo compound so obtained with 2 molecularproportions of one of the above-defined coupling components, or with 1molecular proportion of each of two of the above-defined couplingcomponents, or with 1 molecular proportion of one of the above definedcoupling components and with 1 molecular proportion of a couplingcomponent not containing an amino group. As examples of such aromaticdiamines there may be mentioned benzidine, 3:3-dimethoxybenzidine,benzidine- 2:2-disulphonic acid, benzidine-3:3'-dicarboxylic acid,benzidine-3:3'-diglycollic acid and 4:4-diaminostilbene- 2:2-disulphonicacid. Alternatively disazo or polyazo compounds may be obtained by theuse of primary aromatic amines or diamines containing azo groups. Asexamples of such primary aromatic amines or diamines containing azogroups which may be used there may be mentioned4-arninoazobenzene-4'-sulphonic acid, 4'-amino-2-methylphenylazo-2-naphthalene-4:8-disulphonic acid and4-amino-5methoxy-2-methyl-4-nitro 2 sulphoazobenzene.

A similar method of obtaining the dyestuff compounds of the azo serieswhich may be used in the process of the invention comprises coupling acoupling component which optionally contains an NHR group with adiazonium compound which contains an NHR group. Such diazonium compoundsmay be obtained by methods known from the art, by the diazotisation ofaromatic primary amines containing a second amine group or containing amono-substituted amino group. As examples of such aromatic primaryamines there may be mentioned p-phenylene-diamine,1:4-phenylenediamine-2sulphonic acid, 1:4- phenylenediamine2-carboxylicacid and 1:4-diaminonaphthalene-Z-sulphonic acid. As examples ofcoupling components which may be used in this manner there may bementioned the coupling components listed above and also fi-naphthol,2-naphthol-6- or -7-sulphonic acid, 2- naphthol-3:6- or 6:8-disulphonicacid, 1 naphthol-4-sulphonic acid, 1phenyl-3-methyl-S-pyrazolone,1-(4-sulphophenyl) 3-methyl-5 pyrazolone, 1- 2' 5 -dichloro-4-sulphophenyl)3-methyl-5-pyrazolone, 2-benzoylamine-5-naphthol-7-sulphonic acid, 1benzoylamino-8-naphthol- 3:6- or4:6-disulpl1onic acid, phenol, p-cresol, acetoacetanilide andacetoacet-2-methoxyaniline-S-sulphonic acid.

A further method of obtaining the dyestuif compounds of the azo serieswhich may be used in the process of the invention is to treat an azo orpolyazo compound containing at least one acylamino group With aqueousacid or aqueous alkali in order to cause hydrolysis of the acylammogroup or groups. Such azo or polyazo compounds may be obtained fromaromatic primary amines and/or coupling components containing acylaminogroups. As examples of such aromatic primary amines there may bementioned monoacetylbenzidine,4-amino-1-acetylaminonaphthalene-S-sulphonic acid,4-amino-4'-acetyla1ninodiphenyl-3-sulphonic acid,4-amino-3sulphoacetanilide, 3- amin0-4-sulphoacetanilide and4-amino-4-acetylaminostilbene-2:2'-disulphonic acid, and as examples ofsuch couphng components there may be mentioned2-acetylamino-S-naphthol-7sulphonic acid,Z-N-acetyl-N-methylamino-5naphrthol-7-sulphonic acid, 2-acetylaminoandZ-N-acetyl-N-methylamino-8-naphthol-6-sulphonic acids and1acetyiamino-8-naphthol-3:6- and 4:6-d-isulphonic acids.

As examples of dyestuif compounds of the anthraquinone series which maybe used in the process of the invention there may be mentionedanthraquinone compounds containing a group of the formula NHR ashereinbefore defined, attached to an alkylamino or an arylarnino groupwhich is itself attached to an alpha-position of the anthraquinonenucleus. As examples of such anthraquinone compounds there may bementioned 1- amino 4 (4' aminoanilino-)anthraquinone-2:3'-disulphonicacid and the corresponding 2:3z5- and 2:326-trisulphonic acids,1-amino-4-(4"-amin-o-4'-benzoyl-arninoanilino)aanthraquinone-2:3-disulphonicacid and the corresponding -2:3:5-trisulphonic acid, l-amino-4-[4'-(4"-aminophenylazo-)anilino-] anthraquinone 2:2" S-trisulphonic acid,1-amino-4-(4'-amino-3-carboxyanilino-)anthraquinone-Z:S-disulphonicacid, 1-amino-4-(3'-aminoanilino)anthraquinone-2:4:S-trisulphonic acidand the corresponding 2:4'-disulphonic acid, 1-amino-4-[4-(4"-aminophenyl-)anilino-] anthraquinone 2:3":5 trisulphonic acid,1-amino-4-(4'-methylamino)anilinoanthraquinorle-Z:3'-disulph onic acidand the corresponding 2:3'z5-trisulphonic acid,1-amino-4-(4'-n-butylamino)- anilinoanthraquinone-Z:3'-disu1phonic acid,1-amino-4- (4'-methylamino-3'-carboxyanilino-)anthraquinone-Z-sulphonicacid, 1-amino-4-(3'-beta-hydroxyethylamino)anilinoanthraquinone 2:5disulphonic acid, 1 (4'-aminoanilino) anthraquinone-2:3'-disulphonicacid and 1- amino 4 (4' amino-2'-methoxyanilino) anthraquinone- 2 :3'-disulphonic acid.

Such dyestuff compounds of the anthraquinone series may themselves beobtained from anthraquinone compounds, containing a halogen atom or anitro gnoup attached to the appropriate alpha-position of theanthraqinone nucleus, or from the leuco derivative of a 1:4-dihydroxy,-diaminoor amino-hydroxy-anthraquinone, by interacting the appropriateanthraquinone compound with at least one molecular proportion of analiphatic or an aromatic diamine.

Dyestufi compounds of the phthalocyanine series which may be used in theprocess of the invention are preferably metal-containingphthalocyanines, such as copper phthalocyanine-s, containing at leastone water solubilising group such :as a sulphonic acid group, and atleast one group of the formula NHR as hereinbefore defined. Ihe NHRgroup or groups may be attached directly to the benz-rings of thephthalocyanine nucleus or they may be attached thereto through adivalent bridging radical for example -phenylene-, CO-phe-nylene-, SO-phenylene-, NH-phenylene, S-phenylene-, O-phenylene, CH S-phenylene-,CH O-phenylene-, -CH -phenylene-, SCH -phenylene, sO CH -phenylene,

phenylene, CH NH.CO-pheny1ene-, SOQNRyBlkYlene-, CH NR -alkylene, --CONR-phenylene-CH CONR 'arylene, SO2- and CO. In the above divalent bridgingradicals, R stands for hydrogen, alkyl or :cycloalkyl, aryleue standsfor an aromatic divalent bridging radical wherein the terminal valencebond-s may be attached to the same or difierent nuclei, and talkylenestands for an aliphatic divalent radical which may include hetero-atomssuch as nitrogen as Well as carbon in the chain of atoms, for example itmay stand for the radical --CH CH -NHCH CH and the phenylene groups maybe substituted for example by halogen, \alkyl and allcoxy.

As examples of aromatic divalent bridging radicals denoted by arylenethere may be mentioned aromatic nuclei,

for example a benzene nucleus, at napthalene nucleus, an acridinenucleus and a carbazole nucleus, which nuclei may bear furthersubstituents, and radicals of the formula:

wherein the benzene rings may bear further substituents and wherein D-stands for a bridging group, for example CI-I =CH, NH-, -S, -O, SO--N0=N--, --N=N-, NH.CO.NH, CO.NH--, --O.CH CH O'- and As specificexamples of dyestuff compounds of the phthalocyanine series which may beused in the process of the invention there may be mentioned copperphthalocyanine 4 N-(4-amino-3-sulphophenyl-)sulphonamide-4':4":4"'-trisulphonic acid, cobalt, phthalocyanine-4:4'- di N(3-amino-4'-sulphophenyl-)carbonamide-4":4"- dicarboxylic acid andcopper -4-(4-amino-3'-sulphobenzoyl-)phthal-ocyanine.

There may also be used mixtures of aminophthalocyanines, for examplethere may be used a mixture of approximately equal parts of copperphthalocyanine-N-(4- amino-3-sulphophenyl-)sulphonamide trisulphonicacid and copper phthalocyanine di-N- (4-amino-3-sulphophenyl-)sulphonamide disulphonic acid.

The amin-ophthalocyanines which contain a sulphonic acid can be obtainedeither by the sulphonation of known phthalocyanines containing primaryor secondary amino groups or by synthesis from mixtures of phthalic acidderivatives and sulphonated phthalic acid derivatives. 'lhus treatmentwith a sulphonating agent for example .oleurn such as a 20% solution ofsulphur trioxide in sulphuric acid of the amines described in UnitedKingdom specifications Nos. 569,200 and 589,118 gives suitableamino-phthalocyanines. The arninophthalocyanine compounds so obtainedare those containing the divalent bridging radical -phenylene-,COphenylene-, SO -phenylene-, NH-phenylene-, S-phenylene, O-phenylene,

CH S-phenylene- --CH O-phenylene-, CH -phenylene, sCH -phenyleneand --SOCH -phenylene.

Those aminophthalocyani-ne compounds which contain the divalent bridgingradicals mentioned in the last paragraph and also those containing NkCO-phenylene, SO -NR -phenylene-, NR SO -phenylene-, and S0 0- phenylenelinkages as bridging radicals may be obtained by heating togethersuitable derivatives of sulphonated phthalic acid and the substitutedphthalic acids mentioned in the aforesaid United Kingdom specificationsNos. 569,200 and 589,118 by the general methods known to be used for themanufacture of phthalocyanines from suit-able phthalic acid derivatives,for example, by heating together a mixture of 4-sulphophthalic anhydrideand 4- p-nitrobenzoy1phthalic anhydride, urea, cupric chloride andammonium molybdate in o-dichlorobenzene at about 0.; those which containthe CH -link-ag-e may be obtained by sulphonation of the primary andsecondary amines of United Kingdom specifications Nos. 717,137 and724,212; those which contain the CH NR -phenylene-linkage way beobtained by reacting a primary (or secondary N-alkyl orcycloalkyl-)nitroaniline with a phthalocyanine containing chloromethyland sulphonic or carboxylic acid groups obtained by chloromethylation ofa phthalocyanine sulphonic or carboxylic acid, and reducing the productso obtained, for example with sodium sulphide, or by reacting achloro-methyl phthalocyanine with :tor example a diaminobenzenesulphonicacid or carboxylic acid; those which contain the sO NR -alkylenelinkagemay be obtained by reacting a phthalocyanine containing chlorosulphonylgroups with a monoacetyl alkylene diamine in the presence of water, andtreating the product so obtained (which contains both sulphonamide andsulphonic acid groups) with aqueous alkali to hydrolyse the acetylaminogroup; those which contain the SO NR -phenylene-CH -linkage may beobtained in a similar manner by using an amino-N-benzylacetamide inplace of the monoacetylalkylene diamine; those which contain the -CH .NR-al-kylene-linkage may be obtained by reacting a phtalocyaninecontaining chloromethyl and sulphonic or carboxylic acid groups with amonoacetyl alkylene diarnine and treating the product so obtained withaqueous alkali to hydroylse the acetylamino groups; those containing adirect link, so that the amino group is attached directly to thephthalocyanine nucleus, may be obtained by sulphonating theamino-phthalocyanines described in United Kingdom specification No.529,847 or where a starting material containing less than 4 amino groupsattached to the phthalocyanine nucleus is desired, it may be obtained byheating together a mixture of suitable carboxy-or sulphophthalic acidderivatives with one of the substtiuted phthalic acid derivatives usedas starting materials in United Kingdom specification No. 529,847 underconditions known to be used for the manufacture of phthalocyanines fromphthalic acid derivatives, for example by heating the anhydrides withurea and a catalyst, for example ammonium molybdate, in an orgenicsolvent, for example o-dichlorobenzene, and reducing thenitro-phthalocyanine sulphonic or carboxylic acid or hydrolysing theacylaminophthalocyanine sulphonic or carboxylic acid so obtained byknown methods for the conversion or aromatic nitro or acylaminocompounds to the corresponding amines; and those containing the --CO.NR-phenylene-linkage may be obtained by reacting a. phthalocyaninecompound containing carboxylic acid chloride groups with adiaminobenzene sulphonic acid or carboxylic acid or with an aminobenzenesulphonic acid or an aminobeuzoic acid which also contains a nitro groupand reducing the nitro-compound so ob tained; and those containing theCO-NR -phenylene- CH -linkage may be obtained by reacting aphthalocyanine compound containing carboxylic acid chloride groups withan N-aminobenzyl-)acetamide and subsequently hydrolysing the product soobtained with aqueous alkali.

Dyestuff compounds of the nitro series which may be used in the processof the invention are preferably those of the formula:

wherein D stands for a naphthalene or benzene nucleus which may befurther substituted, the nitrogen atom N is in the ortho position to thenitro group, Z stands for hydrogen or for a hydrocarbon radical whichmay be substituted, Q stands for hydrogen or for an organic radicalattached to the nitrogen through a carbon atom, provided that Q and Zare not both hydrogen, and wherein Q may be connected to Z when Z is ahydrcarbon radical or to D, in the ortho position to the nitrogen atomN, to form a heterocyclic ring, and which contain at least one group ofthe formula -NHR, :as hereinbefore defined.

As specific examples of dyestuff compounds cont-aining at least one NHRgroup, as hereinbefore defined, which may be used in the process of theinvention, there may be mentioned the compounds of the following classeswithout, however, limiting the classes to those specifically described.

(1) Monoazo compounds of the formula:

8 wherein D represents an at most di-cyclic aryl radical which is freefrom azo groups and NHR groups, the --NHR group is preferably attachedto the 6-, 7- or 8- position of the naphthalene nucleus, and which maycontain a sulphonic acid group in the 5- or 6-position of thenaphthalene nucleus.

D may represent a radical of the naphthalene or benzene series which isfree from azo substituents, for example a stilbene, diphenyl,benzthiazolylphenyl or diphenylarnine radical. Also in this class are tobe considered the related dyestuffs in which the NHR group, instead ofbeing attached to the naphthalene nucleus, is attached to a benzoylaminoor ianilino group which is attached to the 6-, 7- or 8-position of thenaphthalene nucleus.

Particularly valuable dyestuffs are obtained from those wherein Drepresents a sulphonated phenyl or naphthyl radical, especially thosewhich contain a SO H group in ortho position to the azo link; the phenylradical may be further substituted for example, by halogen atoms such aschlorine, alkyl radicals such as methyl, acylamino groups such asacetylamino and alkoxy radicals such as rnethoxy.

(2) Disazo compounds of Formula IV, wherein D stands for a radical ofthe azobenzene, azonaphthalene or phenylazonaphthalene series and thenaphthalene nucleus is substituted by the NHR group, and optionally bysulphonic acid as in class 1.

(3) Nonoazo compounds of the formula:

wherein D stands for an at most dicyclic aryl radical as described forclass 1 and is preferably a disulphonaphthyl or a 'stil-bene radical,and the benzene nucleus may contain further substituents such as halogenatoms, or alkyl, alkoxy, carboxylic acid and acylamino groups.

(4) Monoor dis-azo compounds of the formula:

wherein D represents an arylene radical such as a radical of theazobenzene, azonaphthalene or phenylazonaphthalene series, or,preferably, an at most dicyclic arylene radical of the benzene ornaphthalene series, and K represents the radical of a naphthol sulphonicacid or the radical of an enolised or enolisable keto-methylene compound(such as an acetoacetarylide or a S-pyrazolone) having the OH group otothe azo group D preferably represents a radical of the benzene seriescontaining a sulphonic acid group.

(5 )Mono or dis-azo compounds of the formula:

wherein D represents a radical of the types defined for D in classes 1and 2 above and K represents the radical of an enolisable ketomethylenecompound (such as an acetoacetarylide or a S-pyrazolone) having the OHgroup in u-position to the azo group.

(6) The metal complex, e.g. the copper, chromium and cobalt complex,compounds of those dyes of Formulae IV, VI and VII (wherein D K and Khave all the respective meanings stated) which contain a metallisable(for example, a hydroxyl, lower alkoxy or carboxylic acid) group orthoto the azo group in D (7) Anthraquinone compounds of the formula:

wherein the anthraquinone nucleus may contain an additional sulphonicacid group in the 5-, 6-, 7- or 8-position and Z represents a bridginggroup which is preferably a divalent radical of the benzene series, forexample phenylene, diphenylene, or 4,4-divalent stilbene or azobenzeneradicals. It is preferred that Z should contain one sulphonic acid groupfor each benzene ring present.

(8) Phthalocyanine compounds of the formula:

wherein Pc represents the phthalocyanine nucleus preferably of copperphthalocyanine, represents OH and/ or -NH Z represents a bridging group,preferably an aliphatic, cycloaliphatic or aromatic bridging group, nand In each represent 1, 2 or 3 and may be the same or diiferentprovided that n-l-m is not greater than 4.

(9) Nitro dyestuiTs of the formula:

wherein V and B represent monocyclic aryl nuclei, the nitro group in Vbeing ortho to the NH group.

In class 1:

6 amino 1 hydroxy 2 (2' sulphophenylazo)- naphthalene-3-sulphonic acid,

6 methylamino --1 hydroxy 2 (4 acetylamino- 2sulphophenylazo)naphthalene 3 sulphonic acid,

8 amino 1 hydroxy 2 (2 sulphophenylazo)- naphthalene3 :6-disulphonicacid,

8 amino l hydroxy 2 (4 chlo-ro 2 sulphophenylazo -naphthalene-35disulphonic acid,

7 amino 2 (2z5 disulphophenylazo) 1 hydroxynaphthalene-3-su1phonic acid,

7 methylamino 2 (2' sulphophenylazo) 1 hydroxynaphthalene-3-sulphonicacid,

7 methylamino 2 (4 methoxy 2sulphophenylazo)-1-hydroxynaphthalene-3-sulphonic acid,

8 (3' aminobenzoylamino)1 hydroxy 2 (2- sulphophenylazo)naphthalene 3:6disulphonic acid,

8 amino l hydroxy 2:2 azonaphthalene- 1' 3 5' 6-tetrasulphonic acid,

8 amino 1 hydroxy 2:2 azonaphthalene- 1 3 5 '-trisulphonic acid,

6 amino 1 hydroxy 2:2 azonaphthalene- 1',3,5-trisulphoric acid,

6 methylamino 1 hydroxy 2:2 azonaphthalene-1',3,5-trisulphonic acid,

7 amino 1 hydroxy 2,2 azonaphthalene 1',3-

disulphonic acid,

8 amino 1 hydroxy 2 (4 hydroxy 3'carboxyphenylazo)-naphthalene-3,6-disulphonic acid,

6 amino hydroxy 2 (4' hydroxy 3'carboxyphenylazo)-naphthalene-3,S-disulphonic acid.

In class 2:

8 amino 1 hydroxy 2 [4' (2" sulphophenylazo) 2' methoxy 5'methylphenylazo1naphtha1ene-3,6-disulphonic acid,

8 amino 1 hydroxy 2 [4 (4" methoxyphenylazo) 2carboxyphenylazo]naphthalene 3,6- disulphonic acid,

8 amino 1 hydroxy 2 [4' (2" hydroxy 3",- 6" disulpho 1 naphthylazo) 2"carboxyphenylazo]naphthalene-3,6-disulphonic acid,

4,4 bis(8" amino l hydroxy 3",6"disulpho-2"-naphthylazo)-3,3'-dimethoxydipheny1,

6 amino 1 hydroxy 2 [4 (2" sulphophenylazo) 2 methoxy 5methylphenylazoJnaphthalene-3,5-disulphonic acid.

In class 3:

2 (4 amino 2 methylphenylazo)naphthalene- 4z8-disulphonic acid, 2 V

2 (4' amino 2 acetylaminophenylazo)naphthalene-5 7-disulphonic acid,

4 nitro 4 (4" methylaminophenylazo)stilbene- 2,2-disulphonic acid,

4 nitro 4 (4" amino 2 methyl 5 methoxyphenylazo) stilbene 2,2disulphonic acid,

4 amino 4' (4" methoxyphenylazo)stilbene- 2,2'-disulphonic acid,

4 amino 2 methylazobenzene 2 5' disulphonic .acid.

In class 4:

1 (2',5 dich1oro-4' sulphophenyl) 3 methyl- 4 (3" amino 4sulphophenylazo) 5 pyrazolone,

1 (4 sulphophenyl) 3 carboxy 4 (4"- amino-3 -sulphophenylazo)-5-pyrazo1one,

1 (2 methyl 5 sulphophenyl) 3 methyl 4- (4 '-amino-3 -sulphophenylazo-5-pyrazolone,

1 (2' sulphophenyl) 3- methyl 4 -(3" amino- 4"-sulphophenylazo-5-pyrazolone,

4 amino 4 (3 methyl 1 phenyl 4 pyra- 201-5"-onylazo)-stilbene-2,2-disulphonic acid,

4 amino 4 (2" hydroxy 3",6" disulpho l"-naphthylazo)-stilbene-2,2-disulphonic acid,

8 acetylamino 1 hydroxy 2 (3 amino 4'- sulphophenylazo)naphthalene 3,6disulphonic acid,

7 (3' sulphophenylamino) 1 hydroxy 2 (4'- amino 2carboxyphenylazo)naphthalene 3- sulphonic acid,

8 phenylamino 1 -hydroxy 2 (4 amino 2- sulphophenylazo)naphthalene 3,6disulphonic acid,

6 acetylamino 1 hydroxy 2 (5 amino 2-sulphophenylazo)naphthalene-3-sulphonic acid In class 5:

1 (3' aminophenyl) 3 methyl 4 -(2'z5 disulphophenylazo) 5 pyrazolone,

1 (3' aminophenyl) 3 carboxy 4 (2' carboxy-4'-sulphophenylazo-5-pyrazolone,

4 amino 4 [3" methyl 4" (2",5"' disulphophenylazo) 1" pyrazol 5" onyl]stilbene- 2,2-disulphonic acid,

1 (3' aminophenyl) 3 carboxy 4 [4" (2',- 5'' disulphophenylazo) 2"methoxy v5"- methylphenyl azo]-5-pyrazolone.

In class 6:

The copper complex of 8-amino-1-hydroxy-2-(2'-hydroxy 5"sulphophenylazo)naphthalene 3:6- disulphonic acid,

The copper complex of 6-amino-l-hydroxy-2-(2'-hydroxy 5'sulphophenylazo)naphthalene 3 sulphonic acid,

The copper complex of 6-amino-l-hydroxy-2-(2-hydroxy 5'sulphophenylazo)naphthalene 3,5- disulphonic acid,

The copper complex of 8-amino-l-hydroxy-2-(2-hydroxy 3 chloro 5'sulphopheny1azo)naphthalene-3,6-disulphonic acid,

The copper complex of G-methylamino-l-hydroxy-Z- =(2 carboxy 5'sulphophenylazo)naphthalene-S- sulphonic acid,

The copper complex of 8-amin0-1-hydroxy-2-[4- (2" sulphophenylazo) 2'methoxy 5 methylphenylazo]-naphthalene-3,6-disulphonic acid,

The copper complex of 6-amino-1-hydroxy-2-[4 (2",5" disulphophenylazo)2' methoxy -'5'- methylphenylazo] naphthalene-3,5 disulphonic acid,

The copper complex of 1-(3-amino-4-sulphophenyl) 3 methyl 4 [4" (2',5"disulphophenylazo) 2" methoxy 5" methylphenylazo] 5- pyrazolone,

The copper complex of 7 (4' amino 3' sulphoanilino) 1 hydroxy 2 [4"(2,5" disul- 1 l phophenylazo) 2" methoxymethylphenylazo]naphthaleue-3-sulphonic acid,

The copper complex of 6-(4-amino-3'-sulphoanilino) 1 hydroxy 2 (2"carboxyphenylazo)- naphthalene-S-sulphonic acid,

The 1:2-chromium complex of 7-amino-6'-nitro-l,2'- dihydroxy 2:1azonaphthalene 3,4 disulphonic acid,

The 1:2-chromium complex of 6-amino-l-hydroxy- 2 (2carboxyphenylazo)naphthalene 3 sulphonic acid,

The 1:2-chromium complex of 8-amino-1-hydroxy- 2 (4' nitro 2hydroxyphenylazo)naphthalene-3,6-disulphonic acid,

The 1:2-cobalt complex of 6-(4-amino-3-sulphoanilino 1 hydroxy 2 (5"chloro 2" hydroxyphenylazo) naphthalene-3-sulphonic acid,

The 1:2-chromium complex of 1-(3-amino-4-sulphophenyl) -3 methyl 4) 2"hydroxy 4"- sulphol "-naphthylazo) 5-pyrazolone,

The 1:2-chromium complex of 7-(4-sulphoanilino)- l hydroxy 2 (4" amino2" carboxyphenylazo)naphthalene-3-sulphonic acid,

The 1:2-chrornium complex of 1-(3'-aminophenyl)- 3 methyl 4 (4" nitro 2"carboxyphenylazo) 5-pyrazolone.

In class 7:

1 amino 4 (3' amino 4 sulphoanilino)anthraquinone-Z-sulphonic acid,

1 amino 4 (4 amino 3 sulphoanilino)anthraquinone-Z,S-disulphonic acid,

1 amino 4 [4 (4" amino 3" sulphophenyl)- anilino] anthraquinone-ZS-disulphonic acid,

1 amino 4 [4' (4" amino 2" sulphophenylazo) anilino] anthraquinone-ZS-disulphonic acid,

1 amino 4 (4' methylamino 3' sulphoanilino) anthraquinone-Z-sulphonicacid,

In class 8:

3 (3 amino 4' sulphophenyl)sulphamy1 copperphthalocyanine-tri-3sulphonic acid,

Di 4 (3' amino 4 sulphophenyl)sulphamyl copperphthalocyanine-di-4-sulphonic acid,

3 (3 aminophenylsulphamyl) 3 sulphamyl-copperphthalocyanine-di-3-sulphonic acid.

In class 9:

4 amino 2' nitro diphenylamine 3,4 disulphonic acid.

According to a further feature of the invention there is provided amodified process for the manufacture of the new dyestuffs, asherinbefore defined, which are aZo dyestuffs containing at least onegroup of Formula I, as hereinbefore defined, which comprises diazotisinga diazotisable primary amine and coupling the diazo compound so obtainedwith a coupling component, either the primary amine or the couplingcomponent or both containing at least one group of Formula I.

This modified process of the invention may be conveniently brought aboutby adding sodium nitrite to a solution or suspension of the primaryamine, which may be an aminoazo compound, in a dilute aqueous solutionof hydrochloric acid, adding the diazo solution of suspension soobtained to an aqueous solution of the coupling component and filteringoff the dyestufi which is precipitated. If necessary sodium chloride canbe added to ensure complete precipitation of all the azo dyestufi.

Those primary amines and coupling components which contain at least onegroup of Formula I may be obtained by condensing the correspondingprimary amine or coupling component containing at least one AH groupwith a pyrimidine of Formula III.

According to a further feature of the invention there is provided amodified proces for the manufacture of the new dyestufis, ashereinbefore defined, wherein one of Y and Y represents a chlorine or abromine atom and the other Y or Y represents a -SCN group or a group ofthe formula:

s R H S.GN

wherein R and R" have the meanings stated above, which comprisestreating a new dyestuff, as hereinbefore delfined, wherein both Y and Yrepresent chlorine or bromine atoms with a compound of the formula:W.SCN or wherein R and R" have the meanings stated above and Wrepresents a hydrogen or a metal atom.

As examples of the metal atoms represented by W there may be mentionedalkali metal atoms such as sodium and potassium.

This modified process of the invention may be conveniently brought aboutby stirring the two reactants together in water, or in a Water-miscibleorganic liquid or in a mixture of water and a water-miscible organicliquid, preferably at a temperature between 30 and C., adding waterand/or sodium chloride and isolating the dyestuif which is precipitated.

As examples of compounds of the formula: W.SCN or which may be used inthis modified process of the invention there may be mentioned sodiumthiocyanate, potassium thiocyanate, sodium diethyldithiocarbamate,sodium N-methylN-phenyldithiocarbamate, sodiumN-ethyl-N-npropyldithiocarbamate and potassium dimethyldithiocarbamate.

If desired the new dyestufis, as hereinbefore defined, can be isolatedfrom the medium in which they have been formed and/or subsequently driedin the presence of a buffering agent. As examples of buffering agentswhich can be used for this purpose there may be mentioned bufferingagents derived from phosphates such as sodium dihydrogen phsophate anddisodium hydrogen phosphate, citrates such as sodium citrate, borates,and alkali metal salts of dialkylmetanilic acid such as sodiumdiethylmetanilate, which are preferably used in conjunction with sodiumhydrogen sulphate.

A preferred class of the new dyestuffs of the invention are thewater-soluble dyestuffs which contain at least one carboxylic acid orsulphonic acid group and which contain one or two groups of the formula:

(halogen) m wherein R has the meaning stated above, halogen represents abromine or preferably a chlorine atom and m represents 1 or 2.

The new dyestutfs, as hereinbefore defined, are valuable for colouringnatural and artificial textile materials for example textile materialscomprising cotton, viscose rayon, regenerated cellulose, wool, silk,cellulose acetate, polyamides, polyacrylonitrile, modifiedpolyacrylonitrile, and aromatic polyester fibres. For this purpose thedyestuffs can be applied to the textile materials by dyeing, padding orprinting using printing pastes containing the conventional thickeningagents or oil-in-water emulsions or water-in-oil emulsions, whereby thetextile materials are coloured in bright shades possessing excellentfastness to wet treatments such as washing, and to light.

The new dyestuffs which contain water-solubilizing groups, for examplesol-phonic acid and carboxylic acid groups, which render them soluble inwater are particularly valuable valuable for colouring cellulose textilematerials. For this purpose the dyestuffs are preferably applied to thecellulose textile material in conjunction with a treatment with anacid-binding agent, for example sodium carbonate, sodium metasilicate,trisodium phosphate or sodium hydroxide, which may be applied to thecellulose textile material before, during or after the ap plication ofthe dyestuff. Alternatively when the dyed textile material is to besubsequently heated or steamed a substance such as sodium bicarbonate orsodium trichloroacetate, which on heating or steaming liberates anacid-binding agent can be used.

For example the cellulose textile material can be coloured by treatingthe cellulose textile material with an aqueous solution or suspension ofthe acid-binding agent and then immersing the so treated cellulosetextile material in a dyebath comprising a solution of one or more ofthe new dyestuffs, as hereinbefore defined, at a temperature of betweenand 100 C., removing the dyed cellulose textile material from thedyebath and if desired subjecting the dyed cellulose textile material toa treatment in a hot aqueous solution of soap.

If desired the cellulose textile material which has been treated with anaqueous solution or suspension of the acid-binding agent may be passedbetween rollers to remove excess aqueous solution or suspension of theacidbinding agent and/or dried before being treated with the aqueoussolution of the said dyestuffs.

Alternatively the aqueous solution of the dyestufi may be applied bypadding to the cellulose textile material which has been treated withthe acid-binding agent and the cellulose textile material then passedthrough rollers and subsequently subjected to the action of heat orsteam. Alternatively the cellulose textile material can be padded withan aqueous solution of one or more 'of the new dyestuffs, ashereinbefore defined, which also contains an acid-binding agent, passingthe so treated cellulose textile material through rollers, then ifdesired drying the cellulose textile material at a suitable temperature,tor example 70 C., and then subjecting the cellulose textile material tothe action of heat or steam. Alternatively the cellulose textilematerial can be dyed by immersing it in a dyebath comprising an aqueoussolution of the one or more of the said dyestuffs which also contains anacidbinding agent, at a suitable temperature for example between 0 and100 C., and thereafter removing the cellulose textile material irom thedyebath, if desired subjecting it to a treatment in a hot aqueoussolution of soap and finally drying the dyed cellulose textile material.Alternatively the aqueous solution of the one or more of the saiddye-stuffs can be applied to the cellulose textile material by a dyeingor a padding method and the coloured cellulose textile materialsubsequently immersed in an aqueous solution or suspension of theacid-binding agent, preferably at a temperature between 50 C. and 100C., or alternatively the coloured cellulose textile material may bepadded with an aqueous solution or suspension of the acid-binding agent,the textile material dried and then subjected to the action of heat orsteam. Alternatively the cellulose textile material can be dyed byimmersing it in a dyebath comprising an aqueous solution or" one or moreof the said dyestuffs, preferably at a temperature between 20 and 100C., and, after the textile material has absorbed some or all of thedyestuffs, adding an acidbinding agent and proceeding with the dyeing atthe same or a different temperature.

The concentration of the acid-binding agent present in the aqueoussolution or suspension of the acid-binding agent or in the aqueoussolution of the dyestuffs is not critical but it is preferred to usebetween 0.1% and of the acid-binding agent based on the total weight ofthe said aqueous solutions or suspension. If desired the 14 aqueoussolution or suspension of the acid binding agent may also containfurther substances, for example electrolytes such as sodium sulphate.

The aqueous solution of the one or more of the said dyestuffs may alsocontain substances which are known to assist the application ofdyestuffs to textile materials, for example sodium chloride, sodiumsulphate, urea, dispersing agents, surface active agents, sodiumalginate or an emulsion of an organic liquid, for exampletrichlo-roethylene in water.

Alternatively the cellulose textile materials can be printed with aprinting paste containing one or more of the new dyestuffs or" theinvention.

This may be conveniently brought about by applying a printing pastecontaining one or more of said dyestuffs to a cellulose textile materialwhich has been impregnated with an acid-binding agent and thereaftersubjecting the printed cellulose textile material to the action of heator steam. Alternatively a printing paste containing one or more of thesaid dyestuffs and containing an acid-binding agent can be applied tothe cellulose textile material and the printed cellulose textilematerial subsequently subjected to the action of heat or steam.Alternatively a printing paste containing one or more of the saiddyestuffs can be applied to the cellulose textile material which issubsequently immersed in a hot aqueous solution or suspension of theacid-binding agent or alternatively the printed textile material isimpregnated with an aqueous solution or suspension of the acid-bindingagent and subsequently subjected to the action of heat or steam.

After applying the printing paste to the cellulose textile material theprinted textile material may, desired, be dried, for example at atemperature between 20 and C., before the printed textile material issubjected to the action of heat or steam.

The cellulose textile material may be printed with the printing paste byany of the commonly known methods of applying printing pastes to textilematerials, for example by means of roller printing, screen printing,block printing, spray printing or stencil printing. The printing pastesmay also contain the commonly used adjuvants, for example urea,thickening agents, for example methyl cellulose, starch, locust beangum, sodium alginate, water-inoil emulsions, oil-in-water emulsions,surface active agents, sodium m-Ititrobenzene sulphonate, and organicliquids, for example ethanol.

At the conclusion of the dyeing and/ or printing processes it ispreferred to subject the so coloured cellulose textile materials to asoaping treatment, which may be carried out by immersing the colouredcellulose textile materials for a short time, for example 15 minutes, ina hot aqueous solution of soap and/ or detergent, and subsequentlyrinsing the coloured cellulose textile material in water before dryingit.

Those new dyestuffs which do not contain water-solubilising groups forexample sulphonic acid, carboxylic acid, sulphonamide andacylsulphonamide groups are, in general, applied to textile materials inthe form of an aqueous dispersion which may be obtained by gravelmillting the dyestufi with water in the presence of a dispersing agentfor example the sodium salt of sulphonated naphthalene formaldehydecondensation products, sulphosuccinic acid esters, Turkey red oil, alkylphenol/ethylene oxide condensation products, soap and similar surfaceactive materials with or without protective colloids such as dextrin,British gum and water-soluble proteins. If desired the aqueous paste ofthe dyestuff so obtained may be dried to form a re-dispersible powderwhich may be converted to a non-dusting powder by any of the processesknown for forming non-dusting powders.

The new dyestuffs, as hereinbefore defined, can be applied tonitrogemcontai-ning textile materials such as Wool and polyamide textilematerials, from a mildly alkaline, neutral or acid dyebath. The dyeingprocess can be carried out at a constant or substantially constant pH,that is to say the pH of the dyebath remains constant or substantiallyconstant during the dyeing process, or if desired the pH of the dyebathcan be altered at any stage of the dyeing process by the addition ofacids or acid salts or alkalis or alkaline salts. For example dyeing maybe started at a dyebath pH of about 3.5 to 5.5 and raised during thedyeing process to about 6.5 to 7.5 or higher if desired. The dyebath mayalso contain substances which are commonly used in the dyeing ofnitrogen-containing textile materials. As examples of such substancesthere may be mentioned ammonium acetate, sodium sulphate, ethyltartrate, non-ionic dispersing agents such as condensates of ethyleneoxide with amines, fatty alcohols or phenols, surface active cationicagents such as quaternary ammonium salts for example cetyltrimethylammonium bromide and cetyl pyridinium bromide and organicliquids such as n-butanol and benzyl alcohol.

Alternatively the new dyestuffs, as hereinbefore defined, can be appliedto textile materials, which are preferably cellulose textile materials,in conjunction with a resinforming composition and an acid catalyst, andthis application may be conveniently carried out by treating the textilematerial wtih an aqueous solution containing (a) a new dyestuif, (b) aresin-forming composition and (c) an acid catalyst, optionally dryingthe so-treated textile material, and thereafter baking the textilematerial at a temperature above 100 C., preferably at a temperaturebetween 130 and 170 C. The resulting coloured textile materials haveexcellent fastness to wet treatments such as Washing and to perspirationand the coloured textile materials are resistant to creasing.

The resin-forming compositions present in the said aqueous solution arecompositions known from the literature or used in practice for theproduction of textile materials having finishes resistant to creasing orto shrinking or of modified handle. As examples of such resin-formingcompositions there may be mentioned epoxy resins, polyisocyanates,condensates of formaldehyde with cresols or with acrolein, and, inparticular mixtures comprising the methylol derivatives or lower alkylethers of methylol derivatives of monomeric or polymeric compoundscontaining a plurality of amine or mono substituted amino groups, saidcompounds being known from the art or used in practice for the formationof resins by condensation with formaldehyde. Such compounds include, forexample, monomenic nitrogen compounds such as urea, thiourea,substituted urea and thioureas, dicyandiamide, dicyandiamidine,biguanides, amides, carbamates, allophanates and heterocyclic compoundssuch as aminotriazines, urons, ureins, ureides, imidazolidones,triazones and hydantoins, or mixtures of such compounds, and polymericnitrogen compounds such as the polymeric amides made by the reaction ofdibasic acids with diamines. The lower alkyl ethers of the methylolderivatives of these compounds include for example the methyl, ethyl,propyl and butyl ethers.

The quantity of the resin-forming composition which is present in theaqueous solution usually amounts to between 3% and 30% by weight of theaqueous solution and is preferably between and 20% by weight of theaqueous solution.

As examples of acid catalysts which may be present in the said aqueoussolution there may be mentioned salts of weak bases and strong acidssuch as ammonium chloride, magnesium nitrate, zinc chloride, zincsulphate and amine hydrochlorides, but a preferred class of acidcatalysts are the mineral acid salts of primary or secondary organicamines which contain at least one alkyl chain carrying at least onehydroxy group. As examples of such primary or secondary organic aminesthere may be mentioned ,B-hydroxyethylamine,

N-methyl-N- B-hydroxyethyl) amine, N-ethyl-N- fl-hydroxyethyl amine,'y-hydroxypropylamine,

,B-hydroxypropylamine,

N N-di( fi-hydroxyethyl) amine,

N: N-di (,B-hydroxypropyl) anfine,

5 N-( ,B-hydroxyethyl -aniline,

N fi-hydroxyethyl -benzy1amine,

p v-dilrydroxypropylamine,

N-methylglucarrrine (also known as N-methyl-N-pentahydroxy-n-hexylamine)N-ethylglucamine,

N- fi-hydroxyethyl glucamine,

N-methyl-N(,8 'y-dihydroxypropyl) amine and 2-amino'1 :2 3-propanetriol.

The quantity of the said acid catalyst present in the aqueous solutionusually amounts to between 0.1% and 5.0% by weight of the said aqueoussolution and is preferably between 0.25% and 2.0% by weight.

The invention is illustrated but not limited by the following examplesin which the parts and percentages are by weight:

Example 1 A solution of 6 parts of 5-cyano-2z4:6-trichloropyrimidine in80 parts of dioxan is added, with stirring, to a solution of 11.5 partsof the disodium salt of 2-(4'-arnino-2'-methylphenylazo)naphthalene-4:8-disulphonic acid in 550 parts ofwater and the mixture is then stirred for 2 hours at a temperaturebetween and C., the pH of the mixture being maintained between 6.5 and 7by the addition of a 10% aqueous solution of sodium carbonate. parts ofsodium chloride are then added and the dyestuff which is precipitated isfiltered otf, washed with 20 parts of acetone and dried.

On analysis the dyestuff is found to contain 1.89 atoms of organicallybound chlorine for each molecule of dyestuff. When applied to cellulosetextile materials in conjunction with a treatment with an acid-bindingagent the dyestuif yields reddish-yellow shades possessing very goodfastness to washing and to light.

The 5-cyano-2z4:G-trichloropyrimidine used in the above example may beobtained as follows:

A mixture of 38.4 parts of barbituric acid, 144 parts of urea and 24.1parts of potassium cyanate is stirred at a temperature of 150 C. for 3hours. The mixture is cooled to 100 (3., 24-0 parts of hot water areadded, the mixture is then cooled to 50 C. and parts of a concentratedaqueous solution of hydrochloric acid are added. The mixture is thencooled to 20 C. and the precipitated 5-carbonamidobarbituric acid isfiltered off, washed with water and dried.

28 parts of dimethylaniline are added, with stirring, during 10 minutesto a mixture of 17.1 parts of S-carbonamidobar-bituric acid and parts ofphosphorus oxychloride and the mixture so obtained is then stirred atthe boil under a reflux condenser for 45 minutes. The mixture is thencooled to 20 C. poured on to ice and the precipitated5-cyano-2:4:6-trichloropyrimidine is filtered off, washed with Water anddried. The 5-cyano-2z4:6-trichloropyrimidine can be purified bysublimation at a temperature of 110 C. and at a pressure of 0.1 mm. ofmercury. The pure compound has a melting point between 119 and 121 C.

Example 2 19.7 parts of copper phthalocyanine-3-sulphon-N-(4-aminophenyl)amide 3 sulphonamide 3 sulphonic acid (which may be obtainedas described below) are suspended in 900 parts of water and a 2 Naqueous solution of sodium hydroxide is added until a clear solution isobtained and the pH of the solution is 7. The solution is cooled tobetween 15 and 20 C. and a solution of 4.5 parts of5-cyano-2:4:6-trichloropyrimidine in parts of dioxan is then added. Themixture is stirred for /2 hour at a temperature between 15 and 20 C.whilst maintaining the pH of the mixture between 6 and 7 by the .17addition of a 2 N aqueous solution of sodium hydroxide. 100 parts ofsodium chloride are then added and the precipitated dyestuff is filteredoff and dried.

When applied to cellulose textile materials by a printing process inconjunction with a treatment with an acidbinding agent the dyestuifyields bright greenish-blue prints posses-sing excellent =fastness towet treatments.

The copperphthalocyanine-3-sulphon-N-'(4-aminophenyl)amide-3-sulphonamide-3-sulphonicacid used in the above example may be obtained as follows:

115.2 parts of copper phthalocyanine are slowly added with stirring to540* parts of chlorosulphonic acid and the mixture is then stirred for 3hours at a temperature between 140 and 145 C. The mixture is cooled to80 C., 100 parts of thionyl chloride are added and the mixture is thenstirred ior 2 hours at a temperature of 85 C. The mixture is cooled to20 C., poured on to ice and the precipitated phthalocyaninesulphonchloride is filtered off and washed with 1000 parts of a 1%aqueous solution of hydrochloric acid which has been cooled to C.

The solid sulphonchloride so obtained is stirred'with 1000 parts ofwater and 600 parts of ice and 30 parts of p-aminoacetanilide are thenadded. The pH of the resultant mixture is adjusted to 8 by the additionof a 2 N aqueous solution of ammonium hydroxide and the temperature ofthe mixture is then raised to 50 C. during 1 hour, the pH of the mixturebeing maintained at 8 by further additions of a 2 N aqueous solution ofammonium hydroxide. The mixture is then stirred at a temperature of 50C. until no further additions of ammonium hydroxide solution arerequired to maintain the pH at 8. 500 parts of a concentrated aqueoussolution of hydrochloric acid are then added and the mixture is stirredfor 3 hours at a temperature of 90 C. The mixture is then cooled .to 20C. and the precipitated solid is filtered ofi, washed with a 1% aqueoussolution of hydrochloric acid and dried.

Example 3 then filtered off, washed with 20 parts of acetone and' dried.

On analysis the dyestuii is -found to contain 0.82 atom of hydrolysablechlorine for each molecule of dyestuif. L When applied to cellulosetextile materials in conjunction,

with a treatment with an acid-binding agent the dyestuflf yieldsreddish-yellow shades possessing very good fastness to washing and tolight.

The 2-methyl-5-cyano-4:6-dichloropyrimidine used in the above examplemay be obtained by heating a mixture of 2-methyl-4:6dihydroxypyrimidine,urea and potassium cyanate to give2-methyl-4:6-dihydroxy-S-carbonamidopyrimidine which onheating withphosphorus oxychloride,

as described in volume 48 of Ohemicke Listy at pages 1364 to 13 69,yields 2-methyl-5-cyano-4: 6-dichloropyrimidine.

Example 4 In place of the 4.5 parts of 5-cyano-2:4:6-trichloropyrimidineused in Example 2 there are used 3.9 parts of2-methyl-5-cyano-4:6-dichloropyrimidine or 4.0 parts of5-car-boxy-2:4-dichloropyrimidine (which may be obtained as described involume 20 of the Journal of Organic Chemistry at page 837) or 4.4 partsof S-carbomethoxy- 4:6-dichloropyrimidine (which may be obtained asdescribed in lvolume 20 of the Journal of Organic Chemistry at page 837)or 3.8 parts of.5-cyano-2:4-dichloropyrimi- I8 dine or 7.0 parts of5-cyano-2z4:6-tribromopyridine when similar dyestulfs are obtained.

The 5-cyano-2:4-dichloropyrimidine used in the above example may beobtained as follows:

49 parts of diethylaniline are added, during 15 minutes, to a mixture of25 parts of S-cyanouracil and 42 parts of phosphorus oxychloride and theresulting mix-ture is stirred for 2 hours at the boil under a refluxcondenser. The mixture is then cooled to 20 C., poured on to ice and theresulting aqueous mixture is extracted 5 times using 200 parts of etherfor each extraction. The ether extracts are then washed with water, thenwith an aqueous solution of sodium bicarbonate, and finally dried.- Theresulting solution is then distilled when 5-cyano-2z4-dichloropyrimidinedistills between 136 and 138 C. at a pressure of 23 ms. The product soobtained melts at 62 to 63 C.

The 5-cyano-2:4:6-tribromopyrimidine used in the above examples may beobtained as follows:

30 parts of ethylaniline are added, during 30 minutes, to a mixture of10 parts of 5-carbonamidobarbituric acid and parts of phosphorusoxybromide at a temperature between 50 and 60 C., and the resultingmixture is then stirred for 2 hours at a temperature between and C. Themitxure is then cooled to 20 C., poured on to ice and the precipitated5-cyano-2:4:6-tribromopyrimidine is filtered olf, washed with water anddried. After crystallisation from a petroleum ether (which boils between100 and 120 C.) the product melts at 212 to 214 C.

Example 5 A solution of 9 parts of 5-cyano2z4z6-trichloropyrimidine in50 parts of dioxan is added, with stirring, to a solution of 16.6 partsof the disodium salt of 4-amino-2'- nitrodiphenylamine-3:4-disulphonicacid in 500 parts of water and the resulting mixture is stirred at 20 C.until no further additions of an aqueous solution of sodium hydroxideare required to maintain the pH between 6 and 7. parts of sodiumchloride are then added and the precipitated dyestufi" is filtered ofiand dried.

When applied to cellulose textile materials in conjunction with atreatment with an acid-binding agent the dyestuff yields yellow shadeswhich possess excellent fastness to wet treatments.

Example 6 A solution of 4.4 parts of sodium diethyldithio carbamate and17.4 parts of the dyestufl? of Example 5 in 450 parts of water isstirred for 1% hours at a temperature between 30 and 35 C. 125 parts ofpotassium chloride are added, the mixture is cooled to 20 C. and theprecipitated dyestuff is then filtered off and dried.

On analysis the dyestufl is found to contain 7 nitro gen atoms, 4sulphur atoms and l chlorine atom per molecule of dyestulf.

When applied to cellulose textile materials in conjunction with atreatment with an acid-binding agent the dyestufi yields yellow shadespossessing excellent fastness to wet treatments.

Example 7 A solution of 9.0 parts of sodium diethy ldithiocarbamate and22 parts of the dyestuff of Example 2 in 800 parts of water is stirredfor 45 minutes at a temperature of 60 C. 100 parts of sodium chlorideare then added and the precipitated dyestufi is filtered oil and dried.When applied to cellulose textile materials in conju'n'ction with atreatment with an acid-binding agent the dyestufr" yields blue shadespossessing excellent fastness to light and to wet treatments.

Example 8 A solution of 12.7 parts of the trisodium salt of 1- amino 4(4' aminoanilino)anthraquinone 2:3z5-trisulphonic acid in 200 parts ofwater is added, during 20 minutes, to a solution of 4.22 parts ofS-carbomethoxy- 2:4-dichloropyrimidine in a mixture of 100 parts ofdioxan and 50 parts of water. The mixture is stirred for 90 minutes at atemperature of 40 C., the pH being maintained between and 6 by thegradual addition of a 2 N aqueous solution of sodium carbonate and themixture is then stirred for 3 hours at 50 C. 20 parts of sodium chlorideare added and the precipitated dyestufi is filtered off, washed with asolution of parts of sodium chloride in 200 parts of water, then with100 parts of acetone, and finally dried.

When applied to cellulose textile materials in conjunction with atreatment with an acid-binding agent the dyestuff yields blue shadespossessing excellent fastness to wet treatments.

Example 9 A solution of 12.7 parts of the trisodium salt of 1- amino 4(4 aminoanilino)anthraquinone 2:3z5-trisulphonic acid in 200 parts ofwater is added with stirring to a solution of 4.27 parts of5-cyano-2z4:6-trichloropyrimidine in a mixture of 100 parts of dioxanand 50 parts of water and the resulting mixture is stirred for 1 hour atC., the pH of the mixture being maintained between 5 and 6 by theaddition of a 2 N aqueous solution of sodium carbonate, 40 parts ofsodium chloride are then added and the precipitated dyestuif is filteredoil, washed with a 10% aqueous solution of sodium chloride and dried.

On analysis the dyestufi is found to contain 2 chlorine atoms and 6nitrogen atoms per molecule of dyestuff.

When applied to cellulose textile materials in conjunction with atreatment with an acid-binding agent the dyestulf yields blue shadespossessing excellent fastness to wet treatments.

The following table gives further examples of the new dyestuffs of theinvention which are obtained when the 12.7 parts of the trisodium saltof the anthraquinone compound used in Examples 8 or 9 are replaced byequivalent amounts of the sodium salts of the anthraquinone compoundslisted in the second column of the table and/or the 4.22 parts ofS-carbomethoxy-Z:4-dichloropyrimidine used in Example 8 or the 4.27parts of 5-cyano- 2:4:6-trichloropyrimidine used in Example 9 arereplaced by equivalent amounts of the pyrimidines listed in the thirdcolumn of the table. The fourth column of the table indicates the shadesobtained when the dyestuffs are applied to cellulose textile materialsin conjunction with a treatment with an acid-binding agent.

20 aqueous suspension of diazotised 4-aminoanisole-3-sulphonic acid(which is obtained by diazotising an aqueous solution containing 5.5parts of sodium 4-aminoanisole- 3-sulphonate by known methods) is thenadded during 5 minutes. The resulting mixture is then stirred for 1 /2hours at 5 C. and the precipitated dyestuff is filtered off, washed withacetone and dried. On analysis the dyestuff is found to contain 1.82atoms of organically bound chlorine per molecule of dyestufi. Whenapplied to cellulose textile materials in conjunction with a treatmentwith an acid-binding agent the dyestufi yields scarlet shades possessingvery good tastness to wet treatments.

Example 23 A solution of 5.5 parts of 5-cyano-2z4z6-trichloropyrimidinein a mixture of parts of acetone and 40 parts of dioxan is added to asolution of 5.2 parts of sodium m-phenylenediamine sulphonate in 150parts of water and the resulting mixture is stirred for 1 hour at 40 C.,the pH of the mixture being maintained between 6.5 and 7 by the additionof a 10% aqueous solution of sodium carbonate. The resulting solution isthen cooled to 5 C., and 8 parts of a concentrated aqueous solution ofhydrochloric acid are added followed by a solution of 1.7 parts ofsodium nitrite in 10 parts 'of water. The resulting mixture is stirredfor 5 minutes and is then added to a solution of 8.2 parts of thedisodium salt of l-(4 sulphophenyl)-3-carboxy-5-pyrazolone in parts ofwater at a temperature of 5 C., the pH of the mixture being maintainedat 7.5 by the simultaneous addition of a 10% aqueous solution of sodiumcarbonate. The mixture is then stirred for 30 minutes, 50 parts ofsodium chloride are added and the precipitated dyestuff is filtered oiland dried.

On analysis the dyestuff is found to contain 1.85 atoms of organicallybound chlorine per molecule of dyestuff. When applied to cellulosetextile materials in conjunction with a treatment with an acid-bindingagent the dyestuff yields greenish-yellow shades possessing very goodfastness to wet treatments and to light.

Example 24 A solution of 5.1 parts of 5-cyano-2:4-dichloropyrimidine in50 parts of acetone is added with stirring to a solution of 14.5 partsof the trisodium salt of 1-(3-aminophenyl)-3-carboxy-4-(l:5"-disulphonaphth 2-ylazo)- 5-pyrazolone in 250 parts of water, andthe resulting mix- Ex. Anthraquinone compound Pyrimidine Shade1-amino+(4-aminoanilino)anthraquinone-2:3:5-trisulph0nic acid2-rnethyl-5-cyan0-4:6-dichloropyrimidine Blue. rin5-cyano-2:4-dichloropyrimidine D0. dn 5-cyano-2:4z6-tribromopyrimidineDo. l-amino-4-(4-aminoanilino)anthraquinone-Z:3-disulphonic acid. do Ddn 5-oyano-2:4:fi-trichloropyrlmidine Do.l-amino-i-(3-aminoanilino)anthraquinone-2:4'-disulphonic acid do Do.Mixture of 1-amino-4[4-(4-aminophenylazo)aniline]anthraquinone-2:2:5-and do Olive green.

-2:2:8-trisulphonic acids. d 5-cyano-2:4-dichloropyrimldine Do. do2-methyl-ecyano-4:G-dichloropyrimidine Do. Mixture of 1-amino-4-[4-{B-(4-aminophenyl)vinyll anilino1anthraquinone- .do Green.

2:2:3z5- and -2:2:3:8-tetrasnlph0nic acids. Mixture of 1-arnino-4-[4'-{fl-(4"-aminophenyl) vinyl} anilinolanthraquinone-5-eyano-2z4z6-triehloropyrimidine Do.

2:2 :3z5- and -2:2 z3z8rtetrasulphonic acids. 21 dn 5cyano-2:426tribromopyrln1idine D0.

Example 22 A solution of 5.6 parts of 5-cyano-2:4:6-trichloropyrimidinein a mixture of 30 parts of dioxan and 30 parts of acetone is added,with stirring, to a solution of 6.5 parts of sodium2-amino-5-naphthol-7-sulphonate in 150 parts of water and the resultingmixture is then stirred for 1 hour at a temperature between 40 and 50C., the pH of the mixture being maintained between 6.5 and 7 by theaddition of a 10% aqueous solution of sodium carbonate. The resultingsolution is cooled to 5 C., and an ture is then stirred for 2 hours at25 C., the pH of the mixture being maintained between 6.5 and 7 by theaddition of a 10% aqueous solution of sodium carbonate. The dyestufiwhich is precipitated is then filtered off, washed with acetone anddried.

On analysis the dyestufi is found to contain 1.09 atoms of organicallybound chlorine per molecule of dyestutf. When applied to cellulosetextile materials in conjunction with a treatment with an acid-bindingagent the dyestulf yields greenish-yellow shades possessing very goodfastness to washing and to light.

21 Example 25 A solution of 2.3 parts of5-carbomethoxy-2z4-dichloropyrimidine in a mixture of 20 parts ofacetone and 20 parts of dioxan is added with stirring to a solution of5.99 parts of the trisodium salt of 1-(3'-aminophenyl)-3- 5carboxy-4-('1":5 disulphonaphth 2" yl-azo)-5-pyrazolone in 150 parts'ofwater and the resulting mixture is 7 then stirred for 3 hours at atemperature between 28 and 32 C., the pH of the mixture being maintainedbetween 6.5 and 7 by the addition of a 10% aqueous solution of sodiumcarbonate. 15 parts of sodium chloride are then added and theprecipitated dyestuif is filtered 01f, washed with acetone and dried. 7

On analysis the dyestufl so obtained is found to contain 1.05 atoms oforganically bound chlorine per mole- 22 cule lof dyestulf. When appliedto cellulose textile ma terials in conjunction with a treatment with anacid-binding agent the dyestufi yields greenish-yellow shades whichpossess very good fastness to washing and to light.

The following table gives further examples of the new dyestufis of theinvention which are obtained when the Shade obtained 011 EX- AmillOaZOpound Pyrimidine cellulose textile materials 262-amino-6-(2-sulphophenylazo)-5-naphthol-7-sulph0nic acid 5-cano-2;4:6trichloro yrimidine Oran c 272-amino-7-(2-sulphophenylazo)-8-naphthol-6-sulph0nic acid Zdo p 23 1(2z5 dichloro 4 sulphophenyl) 3 methyl 4 (3 amino-6-su1phdo Y lloophenylazo)-5-pyrazolone.1-(2-ch1ofo-5-sulphopheny1)-3-metl1y1-4-(3"-amino-6-sulphopheny1azo)5-do D pyrazo one.z-amino-fi-(2-su1pho-4-methoxyphenylazo)-5-naphtl1ol-7-sulphonic acid doScarlet, 2-amino-7-(2-su1pho4-methoxyphenylazo)-8-naphthol-6-su1phouicacid fi-cyano- 4:6tribrom0pyrimidine- Red.2-metl1ylamino-7-(2-su1pho-4-meth0xyphenylazo)-8-naphthol-6-sulphomc doR d,

aci 2-amino'5-hydroxy'6:2-azonaphthalene-7:l:5-trisulph0nic acid5-cyano-2:416-trichloropyrimidine Orange.2-methylamino-5-hydroxy-6:2-azonaphthalene-7 :1:5-trisu1phonic acid (l0nafihrqmiu g complex of 2-amino-6-(2'-carboxypheny1azo)5-naphthol-7-su1- do Brown,

p on c aci 36 lzz-lclhromiunii complex 0!2-amino-6-(2-carboxpyhenylazo)-5-naphthol-7-sul-5-cyano-2:4-dichloropyrimidine Do.

p onic aci 37 do 2-methyl-5-cyano-4:G-dichloropyrimidine Do. do5-carboxy-2:4-dichloropyrimidine Do.-nitro4-(4"-N-methylam1nophenylazo)-stilbene-2:2-disulphonic acid5-cyano-2:4z6-trichloropyrimldin Reddish-ycllow.

1:2-chromium complex of 6-amino-1:2-dihydroxy-6-nitro-2:l-azonaphtha-..do Black.

lerie-3:4-disulphonic acid. 2.(3'.amm0-6sulphophenylazo)-1-11aphthol-3:G-disulphonic acid5-cyan0-2z4:6-trichlor0pyrimidine Reddish-orange. 2-amino-6-(3-amino-6-sulphophenylazo)-5-naphthol-7-sulpl1onic acid5-cyan0-2:4:6-tribromopyrimidiue- Orange. 2 alilllillo -16 [2 '&sulpho4' (4 -su1ph0pheny1azo) phenylazo] 5 naphthol (1 Red.

su p on 0 am 2-amino-5-hydroxy-6 2-azonaphthalene-7 4 :8-trisu1phonicacid Scarlet. 2-amino-5hydro xy-6: 2-az0naphthalene-7: 5 7-trisul phonicacid Do.2-(4amino-3'-sulphophenylamino)-6-[2-sulpho4-(p-sulphophenylazo) Violet.

phenylazo -5-naphth0l-7-s11lphonic acid. 2-arnino-7-(3-amino-6-sulphophenylazo)-8-naphthol-6-snlphonic acid Reddish-orange. 2aminc-s-hydroxy-7:2-azonaphthalene-6:4 :8-trisu1phonic acid Red.2-amino-8-hydroxy-7:2'-azonaphthalene-G:1 :5-trisulphonic acid.5-cyano-2-methyl-4:6-dic Red.1-amino-7-(3-sulphophenylazo)-8-naphth01-3zfi-disulphonic acid5-cyauo-2z4z6-trichloropyrimidine Bluish-red. 1amino-7-(2-sulph0-4-chlorophcnylazo)-8-naphthol-3: (i-disulphonic acid dDo. 1-amino-7-(2-su1pho-4-methoxyphcnylazo)-8-naphthol 6 disulphonicacid Rubinc. 1-am1'no-7--ami110-6-sulphophenylazo)-8-napthol-3:fi-disulphonic acid Bluish-rcd.1-amino-7- (2 -sulpl1ophenylazo) -8-naphthol-4: fi-disulphonic acid Red1-amino-8-hydr0Xy-7:2-az0n&phthaleI1e-3:6:1-tliS\11ph0nic acid Rubine. 1a ino-7-(4-sulphophenylazo)-8-naphthol-4 :fi-disulphonic acid doBluish-red. 2-(2-acetylamino-4-aminopheny1az0)-naphthalenc-4:S-disulphonic acid 2-methyl-5-cyano-4z6-dReddish-yellow. 2.(2-m thy1-4-aminophenylazo)naphthalene-5:7-disulphonic acid D pyrazolone. 1-(48-disu1phonaphth-2-y1)-3methyl-4-(3"amino-6-sulphophenylazo)fi-pyrazolone. u1 ho hcny1azo)-2-naphthol-6-sulphomc acid1-(3-ami11o-6-sulphophenylazo)-2-naphthol-6:S-disulphonicacid.2-(3-amino-6-sulphophenylazo)-1-naphthol-3-sulphonic acid aci2-benzoylamino-6-(3-am.ino-6-sulpl1opheny1azo)&naphthol-7-sulphonic acid2-amino-7-(3'-amino-6-sulphophenylazo)-8-naphtho1-6-sulphonic acid 1-(4-ann'no-2-sulphophenylazo)-2-naphthol-8-sulphonic acid p2-acetylamino-6-(4-amino-2-sulphophenylazo)-5-naphthol-7-su1phonic acid2-acetylamino-7-(4'-amino-2-sulphophcnylazo)-8-naphthol-6-sulphonicacid. 1-(4-ami.no-2-su1phophenylazo)-2-amino-S-naphthol-Ersulphonic acid1-acety1amino-7-(4-amino-2-sulpl10phenylazo)-8-napl1thol-3:G-disulphonic sulphonic acid.

2- (3 -amino-6 -sulphophenylazo)-1 :S-dihydroxynaphthalenei65151115136516 n 5-cyaino-2:4-dichloropyrimidine o 5-cya'no-2 :4:6-tribromopyrimidine 5-cyano-2 4: fi-trichloropyrimidineoropyrimidine5-carboxy-2:4-dichloropyrimidine V 5-carbomcthoxy-2:4-dichloropyrimidinc 5-cygno-2- 4- G-trichloropyrimidine o o.Brownish-orange.

Yellow. Do.

Orange. Do.

Do. Bluish-red.

Red. Red.

Red.

Red. Yellowish-red.

Red. Yellowish-red. Red

Blui sh-red.

iolet.

Bordeaux.

Yellow. Red.

Reddish-brown.

Green.

25 Example 140 In place of the 19.7 parts of copper phthalocyanine-3-sulphon-N-(4-aminophenyl)amide 3 sulphonamide-3- sulphonic acid used inExamples 2 or 4 there are used 19.7 parts of copperphthalocyanine-3-sulphon-N-(3'- aminophenyllamided-sulphonamide 3sulphonic acid or 20 parts of copper p-hthalocyanine-3-sulphon-N-(3'-amino-4-methylphenyl)amide 3 sulphonamide-Pr-sulphonic acid or 20.3parts of copperphthalocyanine-3-sulphon-N-(3'-amino-4-methoxyphenyl)amide 3sulphonamide-3-sulphonic acid when similar dyestuffs are obtained.

The above copper phthalocyanines may themselves by obtained by themethod described in Example 2 for the pr-epanation of copperphthalocyanine 3 sulp-hon-N- (4'-aminophenyl)amide 3sulphonamide-3-sulphonic acid except that the 30 parts ofp-a-minoacetanilide are replaced by 30 parts of m-aminoacetanilide or by32.8 parts of 3-amino-6-methylacetanilide or by 36.0 parts of3-arnino-6-methoxyacetanilide respectively.

Example 141 In place of the 19.7 parts of copper phthalocyam'ne-3-sulpl1on-N-(4-aminophenyl)amide 3 sulphonamide- 3-sulphonic acid usedin Examples 2 or 4 there are used 19.7 parts of copper phlthalocyanine 4sulphonN- 3'-aminophenyl)amide-4-sulphonamide-4-sulphonic acid or 19.7parts of copper ph-thal-ocyanin 'e-4su1phon-N-(4'- |aminophenyl)amide 4sulphonamide-4-sulpl1onic acid when similar dyestuffs are obtained.

The copper phthalocyanines used in the above example may be obtained asfollows:

196.8 parts of the tetrasodium salt of copper phthalocyaninetetra-4-sulphonic acid are slowly added with stirring to 970 parts ofchlorosulphonic acid and the mixture is then stirred for 3 hours at atemperature between 115 and 120 C. The mixture is cooled to atemperature of 80 C., 100 parts of thionyl chloride are added and themixture is stirred for 2 hours at a temperature between 115 and 120 C.The mixture is then cooled to 20 C., poured on to ice and theprecipitated phthalocyanine sulphonchloride is filtered off and washedwith 1000 parts of a 10% aqueous solution of hydrochloric acid which hasbeen cooled to C.

The sulphonchloride so obtained is stirred with 1000 parts of water and600 parts of ice and 30 parts of m-aminoacetan-ilide or 30 parts ofp-aminoacetanilide respectively are then added. The pH of the resultingmixture is adjusted to 8 by the addition of a2 N aqueous solution ofammonium hydroxide and the temperature of the mixture is then raised to50 C. during 1 hour, the pH of the mixture being maintained at 8 byfurther additions of a 2 N aqueous solution of ammonium hydroxide. Themixture is then stirred at 50 C. until no further additions of theammonium hydroxide solution are required to maintain the pH at 8. 500parts of a concentrated aqueous solution of hydrochloric acid are thenadded and the mixture is stirred for 4 hours at a temperature of 90 C.The mixture is cooled to 20 C. and the precipitated copperphthalocyanine 4-sulphon-N- (3'- or 4'-aminophenyl)amide 4sulphonamide-4-sulphonic acid is then filtered off and dried.

Example 142 A solutionof 17.4 parts of 5-cyano-2:4-dichloropyrimidine in3 15 parts of acetone is added with stirring to a mixture of 125 partsof water and 125 parts of ice. To the suspension so obtained a solutionof 22.7 parts of Z-hydroxy-5-methyl-4'-aminoazobenzene in 630 parts ofacetone is added dropwise over 30 minutes keeping the temperature below5 C. The slight acidity to Congo red paper which develops is removed byadding 0.2 N sodium carbonate solution. The temperature is allowed torise to 20 C. and the acidity which develops is removed firom time totime by further additions of sodium carbonate solution. When no moreacidity develops the temperature of the reaction mixture is raised to 30C. and the mixture stirred at this temperature for 16 hours. The productis then filtered off, washed with water and dried.

The compound so obtained, when dispersed in aqueous medium, dyespolyamide textile materials in yellow shades of good fastness towashing.

Example 143 -A mixture of 39.72 parts of 2-chloro-4-methanesulphonyl 4(N-fl-hydroxyethyl-N-B-aminoethyl)amino azobenzene, 20.9 parts of5-cyano-2:4:6-trichloropyrimidine, 8.4 parts of sodium bicarbonate and750 parts of acetone is stirred at 30 C. for 2.75 hours and then at 20C. for 18 hours. The product is then precipitated by the gradualaddition of 600 parts of cold water and after stirring for 2 hours isfiltered off, washed with water, and dried.

The compound so obtained, when dispersed in aqueous medium, dyespolyamide textile materials in reddishorange shades of good fastness towashing.

Example 144 A solution of 2.9 parts of 5-cyano-2z4z6-trichloropyrimidinein 20 parts of acetone is added to a solution of 1.36 parts of potassiumthiocyanate in 15 parts of acetone and the resulting mixture is stirredfor 30 minutes at 25 C. The mixture is then filtered and the filtrate soobtained is added, with stirring, to a solution of 6.2 parts of thedisodium salt of 2 amino-6-(2'-sulphopheny-lazo)-5-naphthol-7-sulphonicacid in parts of water, and the resulting mixture is then stirred for 1%hours at 30 C., the pH of the mixture being maintained at 7 by theaddition of a 10% aqueous solution of sodium carbonate. 15 parts ofsodium chloride are then added and the precipitated dyestuflf isfiltered ofi, washed with water and dried.

When applied to cellulose textile materials in conjunction with atreatment with an acid-binding agent the dyestulf yields bright orangeshades possessing excellent fastness to washing and to light.

Example 145 100 parts of a plain weave scoured cotton cloth are paddedthrough an aqueous solution containing 1% of the dyestuff of Example 87,10% of a solution of tetramethylol acetylene diurea, 0.5% of met-hylolstearamide, 0.2% of a non-ionic wetting agent, 0.5 of ammoniumthiocyanate and 0.5% N-methyl glu-camine hydrochloride, and the cloth isthen squeezed between rollers to a weight of 200 parts. The cloth isdried at 70 C. and then baked at 160 C. for 3 minutes. It is then rinsedfor 5 minutes at 80 C. in a solution containing 0.3% sodium carbonateand 0.1% of an anionic detergent. The cloth is finally rinsed in coldwater and dried.

The cloth is coloured a bluish-red shade, which is fast to washing, andthe cloth is resistant to creasing.

Example 146 100 parts of bleached cotton material are padded through anaqueous solution containing 3.0% of the dyestufr of Example 1, 10% ofdimethylol glyoxal monourein, 0.8% of N:N-di(B-hydroxyethyl)aminehydrochloride, 0.-2%- of NzN-diQS-hydroxyethyl)amine, 1%- of methylolstearamide and 0.2% of an alkylated phenol/ ethylene oxide condensate,and the cotton material is then squeezed between rollers until itsweight is 200 parts. i The cotton material is dried at a temperature of70 C. and is then baked for 3 minutes at a temperature of 150 C. Thecotton material is then rinsed in water, immersed for 5 minutes in aboiling aqueous solution containing 0.5 of sodium carbonate and 0.1% ofa mix.-

ture of an alkylated phenol/ethylene oxide condensate and a sulphatedcatty alcohol, rinsed again in water and finally dried.

The cotton material is coloured a reddish-yellow shade which possessesexcellent fastness to light and to wet treatments and the material isresistant to creasing.

Example 147 100 parts of bleached cotton material are padded through anaqueous solution containing 0.5% of the dyestufi of Example 2, 7.5% ofN-hydroxyethyldimethyloltriazone, 2.5% of trimethylol melamine, 1.5% ofN-methylglucamine hydrochloride, 1.0% of methylol stearamide and 0.2% ofan alkylated phenol/ ethylene oxide condensate, and the cotton materialis then squeezed between rollers until its Weight is 200 parts. Thecotton material is dried at a temperature of 70 C. and is then baked for3 minutes at a temperature of 150 C. The cotton material is then rinsedin water, immersed for minutes in a boiling aqueous solution containing0.5% of sodium carbonate and 0.1% of a mixture of an alkylatedphenol/ethylene oxide condensate and a sulphated fatty alcohol, rinsedagain in water and finally dried.

The cotton material is coloured a bright greenish-blue shade whichpossesses excellent fastness to light and to wet treatments and thecotton material is resistant to creasing.

Example 148 100 parts of bleached cotton fabric are padded through anaqueous solution containing 2% of the dyestuif of Example 87, 1% ofsodium bicarbonate and 0.2% of an alkylated phenol/ethylene oxidecondensate, at a temperature of 18 C. and the cotton fabric is thensqueezed between rollers until its weight is 200 parts. The cottonfabric is dried at 70 C. and is then exposed to steam at a temperatureof 102 C. for 1 minute. The coloured cotton fabric is then rinsed inWater, immersed for minutes in a 0.2% aqueous solution of soap, rinsedagain in water and finally dried.

The cotton fabric is thereby coloured a bright bluishred shadepossessing excellent fastness to Washing.

In place of the 2% of the dyestur'f of Example 87 used in the aboveexample there is used 2% of the dyestufi of Example 104 or 2% of thedyestuff of Example 35 Whereby the cotton fabric is coloured in navyblue and brown shades respectively, which possess excellent fastness towashing.

Example 149 100 parts of bleached cotton yarn are immersed in a dyebathcomprising 2 parts of the dyestutf of Example 87 and 90 parts of sodiumchloride dissolved in 3000 parts of water and dyeing is carried out for30 minutes at a temperature of C. 15 parts of sodium carbonate are thenadded and dyeing is continued for 60 minutes at 20 C. The dyed cottonyarn is then removed from the dyebath, rinsed in water, immersed for 5minutes in a 0.2% aqueous solution of a synthetic detergent at atemperature of 100 C., rinsed again in water and finally dried. Thecotton yarn is dyed a brilliant bluish-red shade which is fast towashing.

In place of the 2 parts of the dyestuff of Example 87 used in the aboveexample there are used 2 parts of the dyestuif of Example 26 whereby thecotton yarn is dyed in bright orange shades which possess excellentfastness to washing.

Example 150 100 parts of bleached cotton fabric are padded through anaqueous solution containing 0.2% of the dyestulf of Example 1 and 2% ofsodium carbonate and the cotton fabric is then passed between rollersuntil its weight is 200 parts. The cotton fabric is then rolled up andstored for 4 hours at a temperature of 20 C. The cotton fabric is thenrinsed in Water, immersed for 5 minutes in a 0.2% aqueous solution of asynthetic detergent at a temperature of 100 C., rinsed again in waterand dried. The cotton fabric is coloured a bright reddish-yellow shadepossessing excellent fastness to washing.

23 Example 151 Example 152 A print paste comprising:

Parts The dystuff of Example 26 3 Urea 10 Water 50.5 Sodium bicarbonate1.5 4% aqueous solution of sodium alginate 35 is applied to unmercerisedcotton cloth by machine printing. The printed cotton cloth is dried at atemperature of 70 C. and is then steamed for 6 minutes at a temperatureof 100 C. The printed cotton cloth is then rinsed in water, immersed for10 minutes in a 0.3% aqueous solution of a synthetic detergent at atemperature of 100 C., rinsed again in water and finally dried.

The cotton cloth is thereby printed an orange shade which possessesexcellent fastness to wet treatments.

In place of the unmercerised cotton cloth used in the above examplethere may be used mercerised sateen cloth or viscose rayon cloth whenorange prints are also obtained which possess excellent fastness to wettreatments.

In place of the 3 parts of the dyestulf of Example 26 used in the aboveexample there are used 3 parts of the dyestuff of Example 1, or 3 partsof the dyestuff of Example 35 or 3 parts of the dyestuff of Example 87or 3 parts of the dyestuff of Example 104 or 3 parts of the dyestuff ofExample 55 whereby there are obtained reddishyellow, brown, bluish-red,navy-blue and bluish-red prints respectively which possess excellentfastness to washing.

What we claim is:

1. Process for colouring textile materials which consists essentially intreating the textile materials with a watersoluble dyestuff of theformula:

wherein D is a dyestuif chromophoric radical selected from the classconsisting of azo, anthraquinone, nitro, and phthalocyanine radicals, Ais a member selected from the group consisting of O-, S and NR, Rrepresents a member of the group consisting of hydrogen, substitutedalkyl and unsubstituted alkyl radicals and X represents a pyrimidinering which is attached to A through the carbon atom in one of the 2- and4-positions of the pyrimidine ring, and which carries a substituentselected from the group consisting of cyano, carboxy and carboalkoxygroups attached to the 5-position of the pyrimidine ring, and whichcarries two halogen atoms, selected from the group consisting ofchlorine to bromine atoms, attached to the remaining carbon atoms of thepyrimidine ring, and said group -A-X is attached to a carbon atom in thedyestuff.

2. The process of claim 1 wherein said group of the formula A-X standsfor the group of the formula:

wherein R has the meaning stated in claim 1.

3. Process for colouring cellulose textile materials which comprisestreating the celluloe textile material with a dyestuff which contains atleast one carboxylic or sulphonic acid group and at least one group ofthe formula AX, as defined in claim 1, in conjunction with a treatmentwith an acid-binding agent.

4. Process as claimed in claim 3 wherein the cellulose textile materialis treated with the acid-binding agent before the treatment with thedyestutf.

5. Process as claimed in claim 3 wherein the cellulose textile materialis simultaneously treated with the dyestuff and with the acid-bindingagent.

6. Process as claimed in claim 3 wherein the cellulose textile materialis treated with the acid-binding agent after the cellulose textilematerial has absorbed some or all of the dyestutf.

7. Process as claimed in claim 3 wherein the cellulose textile materialis subsequently subjected to the action of heat or steam.

8. Process for colouring textile materials which comprises treating thetextile material with an aqueous solution containing (a) a Water-solubledyestutf of the formula:

wherein D is a dyestufi chromophoric radical selected from the classconsisting of azo, anthraquinone, nitro, and phthalocyanine chromophoricradicals, A is a member selected from the group consisting of -O, -S andR represents a member of the group consisting of hydrogen, substitutedalkyl and unsubstituted alkyl radicals and X represents a pyrimidinering which is attached to A through the carbon atom in one of the 2- and4-positions of the pyrimidine ring, and which carries a substituentselected from the group consisting of cyano, carboxy and carboalkoxygroups attached to the 5-position of the pyrimidine ring, and whichcarries two halogen atoms, selected from the group consisting ofchlorine to bromine atoms, attached to the remaining carbon atoms of thepyrimidine ring, and said group -A-X is attached to a carbon atom in thedyestutf; (b) a resin-forming composition; and (c) an acid catalyst, andthereafter baking the textile material at a temperature above C.

9. Process as claimed in claim 8 wherein the textile material is acellulose textile material.

References Cited in the file of this patent UNITED STATES PATENTS2,935,506 Heslop et al. May 3, 1960 2,940,817 Browne June 14, 19602,995,412 Kleb Aug. 8, 196 1 FOREIGN PATENTS 822,948 Great Britain Nov.4, 1959

1. PROCESS FOR COLOURING TEXTILE MATERIAL WHICH CONSISTS ESSENTIALLY INTREATING THE TEXTILE MATERIAL WITH A WATERSOLUBLE DYESTUFF OF THEFORMULA: